Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/06—Unsaturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

• the invention relates to molding compositions based on unsaturated polyesters and preferred uses of these molding compositions.
• Impregnating, casting and coating compounds for electrical components such as Motor windings, transformer windings and the like are mostly out Molding compositions built on the basis of unsaturated polyester, which in vinyl and / or allylic unsaturated compounds, such as styrene, ⁇ -methylstyrene, Vinyl toluene, allyl phthalates and monomeric or oligomeric acrylic or Vinyl esters are solved.
• Resin compounds are used as impregnating, casting and coating compounds understood that in electrical engineering according to the generally known methods of Dip soaking, hot dip soaking with subsequent UV / heat curing, the trickling technique, the dip roller process, the flooding process and the potting can be used to impregnate windings, if necessary with additional application of vacuum and / or pressure.
• Impregnation of carrier materials for flat insulating materials such as glass silk, Mica tapes and other absorbent substances and combinations thereof, are understood by this term.
• the hardening can optionally be carried out in the partially cured state can be broken off to further curable prepregs receive.
• a disadvantage of these known molding compositions is the use of the above mentioned unsaturated monomers, which are necessary to adjust the required relatively low processing viscosities and for curing the Unsaturated polyester resins are absolutely necessary. These substances are often Harmful and irritating to the skin. When using impregnants with these substances also frequently have a loss of mass of 20 to 30%. This Significant amounts must be removed from the job in order to Avoid health hazards for workers. The vacuumed Evaporation quantities are usually disposed of in waste air incineration. This creates undesirable emissions. The combustion of these quantities of substances is also uneconomical. Furthermore, there is a risk that this monomeric substances cannot be fully incorporated in the curing. In the residual monomers remaining from hardened masses can be particularly characterized Electrical insulation materials that usually become warm during practical use, leak and lead to unpleasant smells and damage to health. she can also gradually harden in the molding compounds, which Unwanted change in usage properties.
• the unsaturated polyesters with dicyclopentadiene or other 1,3-diolefins to modify the alcohol component as N-hydroxyalkylimides monounsaturated, optionally substituted cycloaliphatic 1,2-dicarboxylic acids contain.
• EP-A-0 118 786 discloses unsaturated molded articles Polyester resins, which may be modified with dicyclopentadiene, cyclopentene or cyclohexene groupings and in a complex, preferably be carried out in two stages. there curing at temperatures above 200 ° C in the presence of radical formers decaying above 140 ° C or by irradiation with accelerated electrons reached.
• the task of the present Invention to provide such molding compositions, the soaking, potting and Coating compounds for electrical insulation can be used have sufficient thermal stability and heat resistance and do not require vinylically unsaturated monomers to dissolve them.
• the molding compositions according to the invention constructed in this way have a sufficiently low processing viscosity and can be excellent through Heat and / or high-energy radiation, such as UV light, can be cured. Very It is also advantageous that they are only extremely small during processing Show mass losses. This means that molding compounds are available which without the usual, further described above as vinylically unsaturated monomers Reactive thinners can be used. However, it is technically possible these known ethylenically unsaturated reactive thinners in subordinate Also use quantities. For example, low styrene Molding compositions are produced, which are still the other advantageous Have properties of the molding compositions according to the invention and the legal limits for styrene concentrations or emissions fall below.
• the molding compositions according to the invention existing, not or only slightly modified plants processed can be.
• the molding compounds are both under high-energy radiation, preferably UV light, as well as radically at room temperature with known ones Combinations of peroxides and co-initiators, for example Heavy metal salts, as well as thermally with free radical initiators, such as Peroxides, azo starters or C-C-labile compounds, curable. It is also possible any combination of the methods mentioned for hardening to use. For example, the molding compositions can first be exposed to UV light the surface hardened and then with compounds that thermally radical ready to be cured under heating.
• the polymeric crosslinkers b) are preferably polyurethanes and in particular preferably polyester which is terminal and / or lateral, based on the Main polymer chain, isoprenyl ether and / or propenyl ether groups and / or Have isoprenyl ester and / or propenyl ester groups.
• the polymer backbone can be linear, arbitrarily branched or dentrimeric. Also in the Main chain only C-C linked connections and connections with chain ether groups are known. Methods for the preparation of 1-propenyl ether are described, for example, in J.V. Crivello et al, in Macromolecular Engineering, Plenum Press, New York, 1995.
• propenyl ethers of polyols such as 1,6-di- (1-propenoxy) decane are available, Tetraethylene glycol di (1-propenyl ether), isopropenylbenzyl-m-isopropyl isocyanate, 1-propenyl glycidyl ether and isoprenol.
• Polyfunctional compounds such as the propenyl ethers mentioned, are used directly as Crosslinker b) can be used.
• isocyanates glycidyl ethers and Isoprenol can build up terminally functionalized polymeric compounds become.
• polyesters and polyurethanes according to the general known rules are available, for example polyurethanes made of isocyanates and with these reactive compounds, preferably hydroxyl compounds or polyfunctional hydroxyl compounds.
• the particularly preferred polyester can thereby achieve the termination according to the invention that the above-mentioned compounds, such as isopropenylbenzyl-m-isopropyl isocyanate, 1-propenylglycidyl ether and isoprenol can also be used.
• the above-mentioned compounds such as isopropenylbenzyl-m-isopropyl isocyanate, 1-propenylglycidyl ether and isoprenol can also be used.
• the structure of the polymeric crosslinker b) makes it possible to use a wide range Range to determine the final properties of the hardened masses.
• Linear Crosslinkers without lateral and with only terminal isoprenyl and / or propenyl groups result in a broader mesh with larger ones Net arch length and greater flexibility of the hardened molding compounds.
• Highly branched and / or laterally highly functionalized crosslinkers result a high crosslinking density and hard or after the molding compounds have hardened also brittle molded articles.
• the polymeric crosslinkers b) are preferably adjusted to be low viscosity and as Reactive thinner for highly condensed, highly viscous, unsaturated Polyester resins a) used. Such combinations result after hardening especially thermostable molded articles.
• the unsaturated polyesters a) or polyester resins - these terms being used synonymously in the sense of the invention - of the molding compositions according to the invention consist of polyester resins known per se, these and / or the polymeric crosslinking agent b) structural units of the general formulas I and / or II, which are derived from dicyclopentadiene (DCPD).
• DCPD dicyclopentadiene
• dihydrodicyclopentadienol according to the general formula VII is commercially available and can also be used in the construction of the unsaturated polyesters. This also introduces the structures of the general formulas I and II and gives unsaturated polyesters a).
• the structure of the polyesters a) is carried out according to those known in the prior art Process for the production of polyesters, usually by polycondensation of multifunctional hydroxyl compounds with multifunctional Acids or their anhydrides at higher temperatures. It can be beneficial be to start from the esters of such compounds and the polyesters Get transesterification at higher temperatures because of such transesterifications sometimes run easier and faster than the direct esterifications.
• the Unsaturated character of the polyester a) arises from the use of unsaturated compounds in the acid and / or unsaturated Alcohol component, for example alkenediols and / or oxalkylated Alkenediols.
• Unsaturated polyester resins a) with maleic acid are preferred or maleic anhydride and / or fumaric acid. These connections are technically available very inexpensively. You can continue by using (with) of multifunctional amines also polyester a) with Amide structures can be obtained. The use of monofunctional Feedstocks are also possible, for example to increase the molecular weight regulate.
• Suitable connections for the construction of the called unsaturated polyester a are adipic acid, suberic acid, Phthalic acid isomers, tetrahydrophthalic acid, endomethylene tetrahydrophthalic acid, Hexahydrophthalic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, Trimellitic acid, pyromellitic acid, ethylene glycol, polyethylene glycols, propylene glycol, Polypropylene glycols, butanediol isomers, hexanediol, neopentyl glycol, trimethylol propane, Glycerin, pentaerythritol, bisphenol A, hydrogenated bisphenol A, OH-polyfunctional polymers, such as hydroxyl group-modified polybutadienes or hydroxyl group-bearing polyurethane prepolymers and epoxy resins, polyfunctional Natural products or their derivatives, such as lins
• Amide and imide structures can also be introduced.
• Such structures are known to the person skilled in the art, for example, from DE-A 15 700 273 and DE-A 17 200 323 are known.
• Such polyester amides or imides can special requirements, e.g. in terms of heat resistance, often better meet as pure polyester.
• Oligo-DCPD mixtures can in a manner known per se by polycycloaddition of cyclopentadiene can be obtained under pressure at temperatures between 170 and 300 ° C.
• the Reaction products can then be worked up by distillation or directly, e.g. with maleic anhydride and water, to the compounds of general Formulas V and VI are implemented.
• polyester produce an excess of acid and then react it with DCPD.
• catalysts such as Boron trifluoride etherate, necessary. At higher temperatures and pressures Oligo-DCPD structures were also formed.
• polyesters a) contain double bonds in the polymer chain, for example as maleic or fumaric acid esters, endomethylene tetrahydrophthalic acid structures according to the general formula VIII are produced by grafting with cyclopentadiene:
• polyester a) from which the Molding compounds are built up special requirements in terms of hardness, Elasticity, viscosity, softening point, etc. be put.
• the polyester is then built up to meet these special requirements the rules known per se to the person skilled in the art. So it is e.g. known the Elasticity of cured polyester resins due to the chain length of the polyols or Vary polycarboxylic acids.
• polyester resins are listed below Using hexanediol or adipic acid have been built up more flexibly than those based on phthalic acid and ethylene glycol.
• polyfunctional substances such as trimellitic acid or trimethylolpropane, the Generate branches in the polyester molecules, known.
• the molding compositions according to the invention can also contain substances included, which are selected from curing accelerators, photoinitiators from Norrish types 1 and 2, other conventional additives, pigments and fillers alone or in any combination with each other.
• the for the polyester a) used thermally after Harden the addition of substances that form radicals when heated.
• Known Radical formers are e.g. Peroxides, azo compounds, azides and C-C labile Fabrics.
• metal coinitiators such as cobalt, manganese, iron, Nickel or lead compounds possible.
• polyesters in the presence of UV initiators of the type the ⁇ -splitter (Norrish type 1) or the H donor / acceptor systems (Norrish type 2) have high UV sensitivity.
• the invention also relates to the use of the invention Molding compound as impregnating, casting or coating compound for components, in particular for electrical or electronic components and as a substrate for flat surfaces Insulating materials.
• casting or coating compounds in the area of Electrical insulation can harden both under high-energy radiation, preferably UV light or by heat below 200 ° C, preferably below of 130 ° C and particularly preferred by combined curing with UV light and heat below 130 ° C. This ensures that the Electrical components do not cure due to high temperatures Insulation materials are destroyed.
• the components can be rationalized Series production can be made because the hardening takes place quickly.
• the curing can also be carried out radically at room temperature using known ones Combinations of peroxides and co-initiators such as heavy metal salts as well by heat with thermally free radical initiators such as peroxides, Azostars or C-C-labile compounds.
• Combinations of peroxides and co-initiators such as heavy metal salts as well by heat with thermally free radical initiators such as peroxides, Azostars or C-C-labile compounds.
• thermally free radical initiators such as peroxides, Azostars or C-C-labile compounds.
• the procedures mentioned any combination can be used for hardening.
• Hardening to a B state i.e. a partially hardened state in which hardening is interrupted and later can be started again is possible.
• a possible combination is, for example, that the molding compound first hardened with UV light on the surface and then with substances that Thermally provide radicals, is further hardened under heating.
• the molding compound as an impregnating, casting or coating compound, i.e. as an insulating compound e.g.
• a process modification can be used in electrical windings gain in importance in which the insulating compound inside the components is initially wholly or partly hardened by electricity, and then under certain circumstances badly hardened surface with UV light -crosslinked, the inside of the Windings can be networked further.
• the template is heated to 90 ° C. An exothermic reaction takes place. Feed 1 is then added at about 116-128 ° C. over 30 minutes and kept at 125 ° C. for one hour. The heating is removed and the addition 1 is stirred in. The mixture is rapidly heated to 130 ° C. under a gentle stream of nitrogen, then the temperature is gradually raised to 190 ° C. within 6 hours and the water of condensation formed is distilled off in the process. A liquid resin with an acid number of 19.8 and a viscosity of 194 Pas / 25 ° C. is obtained.
• polyesters a) prepared in Examples 1 to 3 are improved Stirability heated to 40 ° C and in a ratio of 70:30 with the polymer Crosslinker b) of Example 4 mixed. Then - with the exception of the Mixture of the components from Example 1 and 4 - 4% tert-butyl perbenzoate and 2% "Irgacure 184" (photo initiator, manufacturer CIBA Specialties, Basel) to the total amount added.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Macromonomer-Based Addition Polymer (AREA)

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Citations (6)

• 2001
  • 2001-01-23 EP EP01101161A patent/EP1122282B1/fr not_active Expired - Lifetime
  • 2001-01-23 DE DE50110193T patent/DE50110193D1/de not_active Expired - Lifetime
  • 2001-01-23 ES ES01101161T patent/ES2266027T3/es not_active Expired - Lifetime

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